A Method for the Synthesis of Negatively Charged Manganese Feroxyhyte for the Selective Removal of Mercury from Water

ABSTRACT

The present invention refers to the method for synthesis an absorbent material consisting of a phase of tetravalent manganese feroxyhyte (δ-Fe (1−1) Mn x OOH) with a negatively charged grain surface in which a percentage of iron has been isomorphically substituted by manganese atoms at  0.05 - 25 %. Its&#39; production is carried out in two continuous flow stirred-tank reactors arranged in serial configuration, where mild acidic conditions (pH 5-6) prevail in the first reactor and mild alkaline conditions (pH 9-10) together with high redox potential (600-700 mV) in the second reactor. The material can be used to uptake mercury, as well as other heavy metals from both water and hot gas streams. Specifically, the adsorption capacity is determined by the magnitude of the negative surface charge and the isoelectric point that can be both adjusted by the synthesis process parameters.

The invention belongs to the field of chemical engineering and in particular to water purification technology by means of solid adsorbents. Solid adsorbents are used in the current state of the art as filling media in a column bed for removing by adsorption heavy metal cations and in particular mercury from potable and waste water.

Mercury pollution is considered as one of the most important environmental issues due to its mobility in the various stages of life cycle and its confirmed high toxicity. Exposure to mercury may be particularly harmful depending on the dose taken, the chemical form of mercury, the synergistic effect with other toxic agents and the state of human health. In particular, the main effects observed are chronic poisoning, various reproductive, genetic, neurological and psychiatric problems, as well as side effects in kidneys, blood, urine and limbs. Based on human health concerns about mercury uptake from drinking water, the World Health Organization has already proposed from 1971 and since has been gradually applied worldwide, a concentration of 0.001 mg/L of total mercury, as drinking regulation limit.

The presence of mercury in air, water and soil is related to both natural and anthropogenic processes and activities. In particular, natural processes include the leaching of rocks with minerals containing mercury and air emissions through volcanic or geothermal activity. The main anthropogenic emissions come from fossil fuel combustion, metallurgy, gold mining, waste incineration, as well as from the production of cement, caustic soda, paper and paint. Depending on the acidity, redox potential and concentration of other anions, mercury can be found as bivalent in natural waters and in three forms: Hg²⁺, HgOH⁺ and Hg(OH)₂. However, at the usual pH values of 6-8 the dominant form is Hg(OH)₂.

Mercury removal and capture processes can be classified in those aimed at water purification (mainly wastewater) which focus on ionic forms of mercury and those applied for gas phase purification which usually focus on the volatile metallic form) (Hg⁰). A series of methods for mercury removal such as phyto-absorption, bio-adsorption, artificial wetlands and sedimentation cannot be applied to water intended for human consumption due to the inability to process large flow rates and mainly due to the large volume of toxic wastewater, even though they exhibit acceptable fixed and operating costs. For obvious reasons they cannot be used to remove mercury from flue gases. The use of ion-exchange resins, alumina membranes, polymeric fibers and air stripping exhibit greater efficiency in mercury removal. However, they fall short in terms of operating costs and their inability to process large volumes of water. A wide variety of mercury capture methods has also been used for its removal from gaseous streams and in particular from flue gases. Among these methods are the use of electrostatic or conventional filters, which together with the separation of particulate matter they also remove a percentage of mercury. Catalytic oxidation and the addition of amalgamation reagents, as well as adsorbents spraying, are synergistically used in order to capture mercury and are then separated into electrostatic filters.

However, the most widespread mercury removal technology, both from gas and aqueous streams, is the application of adsorbent materials and mainly activated carbons. The effectiveness of the activated carbons is mainly based on their large specific surface area, whereas the fact that they retain mercury with weak bonds, suggests that they do not have a suitable surface charge density and significant oxidation capacity of elemental mercury, increasing therefore the possibility of future leaching. In addition, the efficiency of activated carbon is considered insufficient on the basis of complying with the new environmental guidelines for both drinking water, where the regulation limit is 1 μg Hg/L, and flue gases where the emission limit is 50 μg Hg/m³.

As a result, in recent years, research has focused on the development of adsorbents based on simple or composite inorganic materials. However, the overwhelming majority of inorganic mercury removal adsorbents are applied to flue gases, and it is often noted that their performance is significantly reduced when applied to water treatment, since water molecules contribute to the reduction of active sites. These cases can be separated:

-   -   in composite materials of two or more phases which act         successively in the oxidation stage of the mercury and at its         capture stage; and     -   in single-phase materials where retention and possible oxidation         of mercury takes place on the surface of the same material.

The first approach is reported by S. Yang et al., Journal of Hazardous Materials 186 (2011) 508, where a composite material of manganese/maghemite (Mn/γ-Fe₂O₃) was used to oxidize mercury from a gas stream and then to its retention either from manganese or maghemite. The ability to retain the oxidized form results from its negative surface load. The maximum capacity is 3.54 mg/g, which it is reduced to 0.52 mg/g when the permitted limit of Hg (50 μg/m³) is reached in the outgoing stream (300° C.).

Sand with adsorbed manganese appears to perform well for water purification from heavy metal as shown in D. A. Atwood and M. K. Zaman, Structure and Bonding, Vol. 120, Springer-Verlag, 163. However, with the pass of fresh water, leaching of the adsorbed mercury is observed.

A similar case is the binary oxide of manganese/zirconium (MnO_(x)/ZrO₂) described in M. M. Wiatros-Motyka et al., Fuel 109 (2013) 559. This material exploits the oxidative capacity of manganese oxide, while the role of zirconium oxide is not elucidated by the authors, but it is likely to provide additional physisorption sites. The data given on the material capacity do not correspond to actual application conditions since the maximum adsorption capacity determined (8.4 mg/g) corresponds to the excessively high effluent concentration of 3000 mg Hg/m³.

The combination of manganese oxide with alumina (MnO_(x)/Al₂O₃) is reported in publication of F. Scala et al., Fuel 108 (2013) 13 and R. A. Jadhav et al., Topical review for U.S. Department of Energy (2005) for the cleaning of hot air from mercury. In the first case, the yield reported for a effluent concentration of around 0.1 mg Hg/m³ is 3.7 mg/g at 200° C., while desorption of mercury is observed at higher temperatures. Therefore, the material is unable to reach the limit of gaseous emissions, while the absorption power is very weak. In contrast, the second article gives evidence confirming the ability to reduce the mercury concentration in the effluent stream below 50 μg/m³ when the temperature is 100° C. The adsorption capacity is relatively low (0.15 mg/g) and decreases rapidly when the temperature rises to 200° C.

A series of binary titanium-oxide based materials (TiO₂) was used in the publications of Y. Li et al., Fuel Processing Technology 89 (2008) 567 (SiO₂/TiO₂), H. Li et al. 2011) 186 and Applied Catalysis B: Environmental 111-112 (2012) 381 (SiO₂/TiO₂/V₂O₅ and MnO_(x)—CeO₂/TiO₂), Q. Wan et al., Chemical Engineering Journal 170 (2011) TiO₂) and S. Wu et al., Fuel 85 (2006) 213 (Fe₂O₃/TiO₂), trying to exploit its catalytic effect on mercury oxidation. However, it is found that in these cases it is necessary to activate the surface of the titanium oxide with ultraviolet radiation together with the co-existence of hydrogen sulphide or hydrochloric acid in the gas stream for the stabilization of the oxidized mercury. Due to these limitations, the process presents significant interferences from other components of the gas stream. In addition, in all cases, although the materials were able to reduce the mercury concentration below the emission limit, the data given on the efficient operation and mercury capacity are incomplete as they refer to a large amount of material and contact times of the gas stream.

The use of iron oxide (Fe₂O_(s)) as an active component is described in the publication of Z. Tan et al., Chemical Engineering Journal 195-196 (2012) 218 in a binary material with silicon oxide (SiO₂), which presents a relatively low yield (85%) in the adsorption of mercury from a gas stream. In this case the oxidation is assisted by the presence of oxygen.

Magnetic ferrite nanoparticles, as a material for water purification from mercury, are proposed in CN 102908992, CN 102872913 and CN 102432085. Nanoparticies are either covered by active mercury adsorption groups (rhodamine, starch) or are incorporated with palladium nanoparticles into carbon nanotubes. In addition to the high cost and incompatibility of rhodamine and starch with potable water, these materials exhibit close to zero mercury uptake efficiency.

A big part of the effort is aimed at upgrading the performance of activated carbon either by incorporating inorganic dopants (MnO₂, ZnCl₂, FeCl₃, CuCl₂) or by activating their surface by oxidation with ozone, hydrogen peroxide, nitric acid and potassium permanganate as reported in the publication of Y. Zheng et al., Progress in Energy and Combustion Science 38 (2012) 599. These materials, even though they multiply the mercury removal capacity of the respective activated carbon, they exhibit a capacity not exceeding 1 mg Hg/g for the effluent concentration of 50 μg Hg/m³.

Document U.S. Pat. No. 8,263,525 B1 discloses a solid carbon nanoparticle substrate and a sequential silicon oxide and sulfide functional coating, which has a significantly higher yield of mercury removal from water compared to corresponding commercial products. The data reported show that the material reaches saturation after 2 hours of water treatment with a concentration of 100 mg/L of mercury. Although the capacity of the material up to saturation is relatively high (50 mg/g), it can be easily concluded that it cannot be applied to potable water where the effluent concentration should be below 1 μg /L.

The second approach involves the use of metals such as Ir, Pt, Pd, Rh, Ti and Ru described in the publication of E. J. Granite et al., Industrial and Engineering Chemistry Research 45 (2006) 4844. These materials, which have the ability to form amalgams with mercury, have been experimentally tested for mercury binding from a hot air stream. The results showed that the yield of Pt reached 100%, Ir was 93% and for the rest did not exceed 65%, while the corresponding adsorption capacities were less than 0.5 mg/g. If the cost of these noble materials is taken into account, their application on a large scale is prohibited.

A series of metal sulphide compounds (e.g.,CuS), which prepared by precipitation of corresponding precursors and an inorganic or organic source of sulphur and used to remove mercury from gasses or liquids, are disclosed in US 20130152788 A1. These materials have a low production cost, however, from measurements provided only for gas adsorption the material capacity corresponds to high effluent concentrations (150-200 μg/m³).

Document US 20130089479 A1 discloses the synthesis of sulphide-based inorganic oxides based on silicon oxide of the general form of (SiO₂)_(x)(OH)_(y)M_(z)S_(a)FB, where M is a metalloid cation, S is a sulphide salt, F is an organosilane and B is a hygroscopic alkali oxide or hydroxide. These complex compounds are used to counteract mercury with the use of the sulphide groups, while at the same time capturing the remaining inhibitory compounds encountered in the flue gases with the use of the other components. Both the cost of the raw materials and the synthesis process is expected to be quite high, and even the evaluation does not show a high mercury removal capacity.

Single-phase materials with relatively high surface cation density have proven to be quite efficient in the adsorption of mercury from gases. Manganese ferrite (Fe_(3−x)Mn_(x)O₄) and non-stoichiometric titanium-magnetite (Fe_(3−x)Ti_(x)O₄) have been studied by S. Yang et al., Environmental Science and Technology 45 (2011) 1540 and S. Yang et al., Applied Materials and Interfaces 3 (2011) 209 in which oxidation of mercury from Ti and Mn⁴⁺, respectively, was verified and then mercury was adsorbed on the surface of the material. These materials are prepared by co-precipitation from iron and manganese or titanium salts. The maximum adsorption capacity reaches 4.0 and 5.1 mg/g, respectively, in a gas stream at a temperature of 250° C. However, when the mercury effluent concentration is less than 0.05 mg/m³, the effective capacity is less than 0.2 mg/m³.

The inorganic adsorbents described in the aforementioned publications as mercury removal materials have the following disadvantages:

-   -   Practically, there is no material aimed for purifying potable         water from mercury. In addition, there is no evidence for the         effectiveness of developed inorganic adsorbents at mercury         removal from hot gaseous streams.     -   Namely, their synthesis processes are of high cost as they are         in a batch operation for long contact time and often under         prolonged heating. In addition, some of the materials used are         of high value.     -   Despite the reported high mercury uptake capacities, these         yields are not meet the drinking water and gas emission         legislative limitations.     -   The low efficiency is due to the fact that the composition is         not designed in such a way that the surface of the material to         exhibit an increased negatively surface charge density, which is         necessary for the irreversible adsorption of positively charged         Hg²⁺ ions found in water.     -   Similarly, oxidation capacity is not optimized, resulting in the         partial adsorption of mercury by physisorption in the form of         Hg⁰, which reduces the yield and allows for subsequent mercury         leaching.     -   The data provided indicate that with the use of these materials         a possible gradual leach of mercury to the environment is         expected, while the corresponding leaching tests are not usually         reported.

Therefore, the development of a mercury-adsorbent with low production cost, a high oxidation capacity of elemental mercury and, above all, a high negatively surface charge density would be the ideal solution for mercury removal for both drinking water and gaseous streams at concentrations below the drinking water regulation limit (1 μg/L), as well as the emission limit (50 μg/m³), respectively, using an adsorption bed.

Several of these characteristics are presented in the manganese tetravalent feroxyhyte described in WO/2012/042282 and in publication S. Tresintsi et al., Environmental Science and Technology 47 (2013) 9699 for the removal of arsenic and other heavy metals as well as mercury from drinking water. This material consists of iron oxy-hydroxide with tetravalent manganese, which gives its high oxidation potential, while being prepared in a continuous and ambient temperature arrangement from low-cost precursor-materials such as FeSO₄ and KMnO₄. However, its' synthesis in an aqueous solution is carried out under acidic conditions (pH 4-7) resulting in a high positive surface charge density as determined by the value of the isoelectric point that exceeds the value of 7. This condition, although it maximizes the removal efficiency of the negatively charged arsenic oxy-anions, limits both the approach and the binding of the positively charged mercury cations due to electrostatic repulsion.

The present invention is based on a new approach to the synthesis process of the tetravalent manganese feroxyhyte (Fe_(1−x)Mn_(x)OOH, where 0.05<x<0.25) that has as the main feature the negatively charged surface (isoelectric point less than 5.5) and high mercury removal efficiency from water, while maintaining oxidative capacity and low production cost. For this purpose, production takes place in a two-stage continuous flow reactor under alkaline conditions (pH 7-12) and strong oxidizing conditions.

The present invention solves the above problems as follows:

-   -   The material has a very high capture capacity of mercury from         water, while at the same time being able to decrease residual         concentration after treatment below the regulation limit of 1         μg/L.     -   It is synthesized in a continuous-flow reactor with high         production capacity from low-cost raw materials at ambient         temperature. Synthesis under alkaline conditions affects         negligibly the cost due to increase the amount of base solution         added, compared to the corresponding material of WO/2012/042282.     -   Its production at alkaline environment (at increased OH⁻         concentration) ensures a high negatively surface charge density,         leading to high adsorption capacity of positively charged forms         of mercury that predominate in water.     -   The oxidative potential due to the presence of tetravalent         manganese favors the complete oxidation of elemental mercury in         the flue gases, as well as in the natural gas at the mining         site, and its capture as Hg²⁺. In this way the maximum removal         efficiency per unit weight of adsorbent is achieved, while at         the same time the phenomenon is irreversible and mercury         leaching into the environment is virtual impossible.

The present invention can be fully understood from the detailed description of the synthesis method, figures and examples of application of the method of synthesis of absorbent material that follows.

The enclosed drawings describe:

The flow diagram of the synthesis process of the adsorbent material according to the described method (Drawing 1).

The schematic representation of the grain growth mechanism of the material during the two reaction steps (Drawing 2).

The correlation diagram of the adsorption capacity, when residual concentration at the limit of 1 μg/L is achieved, of the negatively charged δ-Fe_(0.75)Mn_(0.25)OOH (final synthesis pH 9) for mercury in water with different pH values (5-9) compared to the material prepared entirely in acidic environment (pH 4) Drawing 3).

The correlation diagram of the Hg⁰ adsorption capacity of the negatively charged δ-Fe_(0.75)Mn_(0.25)OOH (final synthesis pH 9) for a residual concentration equal to the limit of 50 μg/m³ as a function of the gas stream temperature compared to the material prepared entirely in acidic environment (pH 4) (Drawing 4).

The correlation diagram of the adsorption capacity, when residual concentration at the limit of 1 μg/L is achieved, of the negatively charged δ-Fe_(0.75)Mn_(0.25)OOH (final composition pH 9) for mercury in water with different pH values (5-9) compared to the material prepared entirely in acidic environment (pH 4) (Drawing 3).

The correlation diagram of the Hg⁰ adsorption capacity of the negatively charged δ-Fe_(0.75)Mn_(0.25)OOH (final composition pH 9) for a residual concentration equal to the limit of 50 μg/m³ as a function of the gas stream temperature compared to the material prepared entirely in acidic environment (pH 4) (Drawing 4).

The purpose of the present invention is to produce a tetravalent manganese feroxyhyte material [Fe_((1−x))Mn_(x)OOH, where 0.05<x<0.25] with an isoelectric point of less than 5.5 and a high negatively surface charge density (1.5 mmol H+/g), which results in high mercury adsorption capacity from water, as well as in high adsorption capacity of other heavy metals with valence ≥+2. This objective was achieved by a reaction of Fe(II) and Mn(VII) salts in a two-stage continuous flow reactors where the following reactions take place:

In the first reactor, the Fe (II) salts are precipitated with KMnO₄ in a weakly acidic to neutral environment for the production of the tetravalent manganese feroxyhyte. The pH is adjusted to a constant value of 5-6 by adding a solution of one of the reagents NaOH, NaHCO₃, Na₂CO₃, KOH, KHCO₃, K₂CO₃, while the high redox potential is set to a constant value of 500±50 mV by adding KMnO₄. The reaction time in the first reactor does not exceed 20 min, which allows the formation of nucleated manganese feroxyhyte, but not the full development of the positive surface structure.

-   -   In the second reactor, the pH is increased with the addition of         either NaOH or KOH in the range between 9 and 10, while the         redox potential is maintained in the 650±50 mV range with the         addition of KMnO₄, so that the increase of the tetravalent         manganese feroxyhyte crystals in a high both pH and redox         potential environment, will lead to the increase of the negative         surface charge, which is necessary for the uptake of the         positively charged ions, such as mercury and other heavy metals.     -   It is then followed by the aging process which takes place in         stirring tank.

More specifically, the synthesis method of the tetravalent manganese feroxyhyte adsorbent with the high negative charge in the pH range of natural waters, corresponding to an isoelectric point lower than 5.5, is performed as follows:

Two continuous flow stirred-tank reactors arranged in serial configuration are used. The retention time in the first reactor does not exceed 20 min (Drawing 1), while in the second reactor is at least 2 hours. The amount of product produced is a function of the iron and manganese reagents flow Q₁, Q₂ to the first reactor and Q₃, Q₄ to the second reactor, respectively. The Q₃ and Q₄ flows can be 0 to 5 times greater than Q₁ and Q₂, respectively.

In the reactor (1) an aqueous solution of FeSO₄ or FeCl₂ of 1-50 g/L concentration and a KMnO₄ aqueous solution of 1-20 g/L concentration are simultaneously introduced in continuous flow. The regulation of the flow rate ratio of the Fe (II) and KMnO₄ solutions is controlled by achieving the desired redox potential of 500±50 mV, which is necessary for the nuclei formation of the Fe_((1−x))Mn_(x)OOH type with the percentage content in Mn(IV) ranging at 12±1 wt %. The reaction product enters the reactor (2), and a new FeSO₄ or FeCl₂ solution of 1-50 g/L concentration and a KMnO₄ solution of 1-20 g/L concentration are added. The regulation of the flow ratio of the Fe (II) and KMnO₄ solutions is controlled by maintaining the desired redox potential of 650±50 mV in the reactor (2). In both reactors (1) and (2), the pH value is adjusted throughout the reaction in the range of 5-6 in the first reactor and in the range of 9-10 in the second one by adding a solution of one or a combination of more than one of the alkaline reagents NaOH, Na₂CO₃, KOH, and K₂CO₃.

The effluent from the reactor (2) is kept in a thickening tank (3) with a gentle stirring for a period of 6-36 hours where maximization and balancing of the negative surface charge is achieved. Under these conditions aging of the granules leads to the formation of amorphous nanocrystals without favoring their agglomeration in secondary morphologies as observed under acidic aging conditions.

The precipitate after thickening is dehydrated by centrifugation (4) and is either molded into 250-2500 μm size granules and dried or first dried and then milled to a grain size of less than 50 μm (5).

The adsorbent material can be used to uptake mercury from water, as well as other heavy metals such as cadmium, lead, nickel, cobalt, vanadium, copper, manganese and iron, preferably in an adsorption bed configuration. Its use is intended for drinking water treatment plants for domestic, industrial and point of use implementation, for the treatment of industrial and municipal waste, as well as for the treatment of flue gases and natural gas.

From the procedure described above the tetravalent manganese feroxyhyte can be formed in the pH range of 3-12. However, at a pH of less than 8, its adsorption capacity for mercury and other heavy metals is dramatically reduced, since the positive surface charge, which repels the homonymous positively charged metal ions, gradually predominates.

In particular, the negatively charged solid tetravalent manganese feroxyhyte has a specific surface area of 200-300 m²/g and a grain size of 250-2500 μm. Its maximum adsorption capacity (q_(max)) for water with a pH of 7-8 exceeds 80 μg Hg/mg at a temperature of 20° C. In addition, the elemental mercury removal rate up to saturation from a gas stream exceeds 50 μg Hg/mg.

The efficiency (parameter q₁) of the material to uptake mercury from natural waters at pH 6-8 and at the same time to achieve at a residual concentration equal to regulation limit of 1 μg/L is obtained from the diagram of Drawing 3. The measurements refer to manganese feroxyhyte with a 25% substitution rate. In these experiments, the test water was prepared according to NSF protocol and its composition reaches the specifications of the majority of natural waters, since it contains all the parameters that inhibit mercury adsorption. In particular, it contains 88.8 mg/L Na⁺, 40 mg/L Ca²⁺, 12.7 mg/L Mg²⁺, 183 mg/L HCO³⁻, 50 mg/L SO₄ ²⁻, 71 mg/L Cl⁻, 2 mg/L N—NO³⁻, 1 mg/L F⁻, 0.04 mg/L P—PO₄ ³⁻ and 20 mg/L SiO₂. The value of parameter q₁ for mercury removal from NSF water, at pH 7, at 20° C. was found to be 2.8 μg/mg. Accordingly, the specific adsorption capacity (q₅₀) for elemental mercury from a gas stream at 120° C. and at an equilibrium concentration of 50 μg/m³, which is the emission limit, was 13.3 μg/mg for contact time of 0.1 s.

Example of Method Application 1

A solution of 45 g/L FeSO₄ H₂O is fed at a flowrate of Q₁=2 m³/h and mixed with a 15 g/L KMnO₄ solution of flowrate Q₂=2 m³/h in the 1 m³ volume stirred-reactor (1). The flowrate of KMnO₄ is varied so that the redox potential in the reactor (1) is maintained at the 500±50 mV range. The pH of the reaction is adjusted to 5.5±0.1 by the addition of 30% w/w NaOH solution.

The reaction product leaving the reactor (1) enters the 16 m³ volume stirred-reactor (2), where a solution of 45 g/L FeSO₄ H₂O at a flowrate of Q₃=2 m³/h and a solution of 15 g/L KMnO₄ at a flowrate of Q₄=2 m³/h are added. The redox potential in the reactor (2) is regulated in the 650±50 mV range by the addition of KMnO₄ and the pH is regulated at 9±0.1 by the addition of a 30% w/w NaOH solution. The product from the reactor (2) outflow is led to the thickening tank where it is kept under mild stirring for 24 hours, then is mechanically dehydrated by centrifuge or filter press, sized to 250-2500 μm and dried at 110° C. The resulting material has a Fe_(0.75)Mn_(0.25)OOH structure and the manganese valence is 4. Its application to an adsorption column with contact time of 3 minutes gives an adsorption capacity of Hg²⁺ 2.8 μg/mg in standard NSF water, pH 7 and an equilibrium concentration of 1 μg/L.

Example of Method Application 2

A solution of 15 g/L FeSO₄ H₂O is fed at a flowrate of Q₁=3 m³/h and mixed with a 15 g/L KMnO₄ solution of flowrate Q₂=1 m³/h in the 1 m³ volume stirred-reactor (1). The flowrate of KMnO₄ is varied so that the redox potential in the reactor (1) is maintained in the 500±50 mV range. The pH of the reaction is adjusted to 5.5±0.1 by adding a 5% w/w K₂CO₃ solution.

The reaction product leaving the reactor (1) enters the 32 m³ volume stirred-reactor (2), where a solution of 15 g/L FeSO₄ H₂O at a flowrate of Q₃=9 m³/h and a solution of 15 g/L KMnO₄ at a flowrate of Q₄=3 m³/h are added. The redox potential in the reactor (2) is regulated in the 650±50 mV range by adding KMnO₄ and the pH is regulated at 9±0.1 by adding a 10% w/w KOH solution. The product from the reactor (2) outflow is led to the thickening tank where it is kept under mild stirring for 24 hours, then is mechanically dehydrated by centrifuge or filter press, sized to 250-2500 μm and dried at 110° C. The resulting material has a Fe_(0.75)Mn_(0.25)OOH structure and the manganese valence is 4. Its application to an adsorption column with contact time of 3 minutes gives an adsorption capacity of Hg²⁺2.8 μg/mg in standard NSF water, pH 7 and an equilibrium concentration of 1 μg/L.

Example of Method Application 3

A solution of 30 g/L FeSO₄ H₂O is fed at a flowrate of Q₁=4 m³/h and mixed with a 20 g/L KMnO₄ solution of flowrate Q₂=2 m³/h in the 2 m³ volume stirred-reactor (1). The flowrate of KMnO₄ is varied so that the redox potential in the reactor (1) is maintained in the 500±50 mV range. The pH of the reaction is adjusted to 5.5±0.1 by the addition of 30% w/w NaOH solution.

The reaction product leaving the reactor (1) enters the 24 m³ volume stirred-reactor (2), where a solution of 30 g/L FeSO₄ H₂O at a flowrate of Q₃=4 m³/h and a solution of 20 g/L KMnO₄ at a flowrate of Q₄=2 m³/h are added. The redox potential in the reactor (2) is regulated in the 650±50 mV range by the addition of KMnO₄ and the pH is regulated at 9±0.1 by the addition of a 30% w/w NaOH solution. The product from the reactor (2) outflow is led to the thickening tank where it is kept under stirring for 24 hours, then is mechanically dehydrated by centrifuge or filter press, sized to less than 50 μm and dried at 110° C. The resulting material has a Fe_(0.75)Mn_(0.25)OOH structure and the manganese valence is 4. Its application to an adsorption column with contact time of 0.01 sec gives an adsorption capacity of Hg²⁺ 13.3 μg/mg for an equilibrium concentration of 50 μg/m³ from a nitrogen gas stream of 120° C.

Example of method Application 4

A 36 g/L FeCl₂ solution is fed at a flowrate of Q₁=12 m³/h and mixed with a 15 g/L KMnO₄ solution with a flowrate of Q₂=4 m³/h in the 5 m³ volume stirred-reactor (1). The flowrate of KMnO₄ is varied so that the redox potential in the reactor (1) is maintained in the 500±50 mV range.

The reaction product leaving the reactor (1) enters the 16 m³ volume stirred-reactor reactor (2), where a solution of 45 g/L FeSO₄ H₂O at a flowrate of Q₃=6 m³/h and a solution of 15 g/L KMnO₄ at a flowrate of Q₄=2 m³/h are added. The redox potential in the reactor (2) is regulated in the 650±50 mV range by the addition of KMnO₄ and the pH is regulated at 9±0.1 by the addition of a 30% w/w NaOH solution. The product from the reactor (2) outflow is led to the thickening tank where it is kept under stirring for 24 hours, then is mechanically dehydrated with a centrifuge or filter press, dried at 110° C. and sized to less than 50 μm. The resulting material has a Fe_(0.75)Mn_(0.25)OOH structure and the manganese valence is 4. Its application by injection into a gaseous nitrogen stream containing Hg⁰ up to 400 μg/m³ resulted in the decrease in its concentration below the emission limit of 50 μg/m³.

Example of Method Application 5

The procedure of Example 3 is followed except that there is no further addition of reactants in the reactor (2). The resulting material has a Fe_(0.75)Mn_(0.25)OOH structure and the manganese valence is 4. Its' application to an adsorption column with contact time of 0.01 seconds gives an adsorption capacity of 10.6 μg/mg for elemental mercury Hg⁰ for an equilibrium concentration of 50 μg/m³ from a nitrogen gas stream of 120° C.

The method described in this invention is performed either on laboratory or industrial scale depending on the production capacity of the continuous flow reactor.

The product produced based on the synthesis method of the invention can be used to capture mercury and other heavy metals such as cadmium, lead, nickel, cobalt, vanadium, copper, manganese and iron from aqueous solution or elemental mercury from a gaseous stream, preferably in an adsorption bed or as powder in an spraying system. 

1. Synthesis method of tetravalent manganese feroxyhyte (δ-Fe_((1−x))Mn_(x)OOH, x=0.05-0.25), characterized by the fact that it is conducted in two continuous flow stirred-tank reactors arranged in serial configuration, where the first reactor has weakly acidic conditions and the second weakly alkaline conditions and high redox potential for the production of a material having a high negative charge surface density, which is applied by the following steps: i) FeSO₄ or FeCl₂is added to the reactor (1) as an iron source at a concentration of 1-50 g/L and KMnO₄ is added as a source of manganese at a concentration of 1-20 g/L to perform the reaction for nuclei production of the δ-Fe_((1−x))Mn_(x)OOH, with the pH value being adjusted to the weakly acidic region of 5-6 by adding one or a combination of more than one of the reagents NaOH, NaHCO₃, Na₂CO₃, KOH, KHCO₃, K₂CO₃, while at the same time the value of the redox potential is adjusted to the range of 450-550 mV with the appropriate adjustment of the FeSO₄ or FeCl₂ and KMnO₄ flowrates, then ii) the reaction of the negatively charged surface nanocrystals growth proceeds to the reactor (2) by further addition of FeSO₄ or FeCl₂ and KMnO₄ reagents with a pH value in the reactor (2) adjusted to the alkaline region 9-10 by adding one or a combination of more than one of the reagents NaOH, KOH and at the same time the value of the redox potential in the 600-700 mV range, with the appropriate adjustment of the FeSO₄ or FeCl₂ and KMnO₄ flowrates, at iii) a residence-reaction time of maximum 20 minutes in the reactor (1) and at least 2 hours in the reactor (2); and iv) the product exiting the reactor (2) enters the thickening tank (3), where with mild stirring for a period of 6-36 hours, grains are formed in an irregular shape, having a specific surface area of 100 m²/g to 300 m²/g, high negative surface charge (>1.5 mmol H⁺/g) and isoelectric point less of than 5.5.
 2. Method according to claim 1, characterized by the fact that its optimal application is achieved when the pH of the reaction is 9 and the redox potential is 650 mV.
 3. Method according to claim 1, characterized by the fact that the produced material undergoes mechanical dehydration (4), granulation at a size of preferably 250-2500 μm and drying at 100-150° C. (5).
 4. Method according to claim 1, characterized by the fact that the material produced after the application of the process is mechanically dehydrated (4), dried at 100-150° C. and granulated in a size of preferably less than 50 μm (5).
 5. Single phase adsorbent material of negatively charged tetravalent manganese feroxyhyte (δ-Fe_((1−x))Mn_(x)OOH) produced according to the method of claim 1, to characterized by the fact that a percentage of 0.05-25% of iron has been isomorphic substituted by manganese atoms, with a specific surface area of 100-300 m²/g, a negative surface charge density greater than 1.5 mmol H⁺/g and an isoelectric point of less than 5.5.
 6. Use of the adsorbent material of claim 5 for uptake in an adsorption bed of mercury and other heavy metals such as cadmium, lead, nickel, cobalt, vanadium, copper and manganese from water.
 7. Use of the adsorbent material of claim 5 for uptake of mercury and other heavy metals such as cadmium, lead, nickel, cobalt, vanadium, copper and manganese from flue gases and natural gas in an adsorption bed or as powder in a spraying system.
 8. Method according to claim 2, characterized by the fact that the produced material undergoes mechanical dehydration (4), granulation at a size of preferably 250-2500 μm and drying at 100-150° C. (5).
 9. Method according to claim 2, characterized by the fact that the material produced after the application of the process is mechanically dehydrated (4), dried at 100-150° C. and granulated in a size of preferably less than 50 μm (5).
 10. Single phase adsorbent material of negatively charged tetravalent manganese feroxyhyte (δ-Fe_((1−x))Mn_(x)OOH) produced according to the method of claim 2, characterized by the fact that a percentage of 0.05-25% of iron has been isomorphic substituted by manganese atoms, with a specific surface area of 100-300 m²/g, a negative surface charge density greater than 1.5 mmol H⁺/g and an isoelectric point of less than 5.5.
 11. Single phase adsorbent material of negatively charged tetravalent manganese feroxyhyte (δ-Fe_((1−x))Mn_(x)OOH) produced according to the method of claim 3, characterized by the fact that a percentage of 0.05-25% of iron has been isomorphic substituted by manganese atoms, with a specific surface area of 100-300 m²/g, a negative surface charge density greater than 1.5 mmol H⁺/g and an isoelectric point of less than 5.5.
 12. Single phase adsorbent material of negatively charged tetravalent manganese feroxyhyte (δ-Fe_((1−x))Mn_(x)OOH) produced according to the method of claim 8, characterized by the fact that a percentage of 0.05-25% of iron has been isomorphic substituted by manganese atoms, with a specific surface area of 100-300 m²/g, a negative surface charge density greater than 1.5 mmol H⁺/g and an isoelectric point of less than 5.5.
 13. Single phase adsorbent material of negatively charged tetravalent manganese feroxyhyte (δ-Fe_((1−x))Mn_(x)OOH) produced according to the method of claim 4, characterized by the fact that a percentage of 0.05-25% of iron has been isomorphic substituted by manganese atoms, with a specific surface area of 100-300 m²/g, a negative surface charge density greater than 1.5 mmol H⁺/g and an isoelectric point of less than 5.5.
 14. Single phase adsorbent material of negatively charged tetravalent manganese feroxyhyte (δ-Fe_((1−x))Mn_(x)OOH) produced according to the method of claim 9, characterized by the fact that a percentage of 0.05-25% of iron has been isomorphic substituted by manganese atoms, with a specific surface area of 100-300 m²/g, a negative surface charge density greater than 1.5 mmol H⁺/g and an isoelectric point of less than 5.5. 